Production of ring polymers from terminal alkynes by alkylidynes

Abstract

This invention relates to a method comprising combining an alkylidyne catalyst compound and a terminal alkyne to form a ring polymer. The terminal alkyne has the formula RC 2 H, wherein R is H, an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, an aromatic group having from 6 to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon atoms, or an alkynyl group having from 2 to 20 carbon atoms. The alkylidyne catalyst compound has the formula (R 1 )(R 2 )(R 3 ) MCR 4 , where M is tungsten or molybdenum, R 1 , R 2 , and R 3 is alkoxide, halide, oxide, nitride, or sulfide, and R 4 is H, an aliphatic group having from 1 to 20 carbons, an aromatic group having from 1 to 20 carbons, or a heteroaryl group having from 1 to 20 carbons, wherein the heteroatom is nitrogen, oxygen, boron, or sulfur.

I claim: 
     
       1. A method of forming a ring polymer, comprising:
 combining an alkylidyne catalyst compound and a terminal alkyne to form a mixture under reaction conditions to form the ring polymer, wherein the alkylidyne catalyst compound has the formula (R 1 )(R 2 )(R 3 )MCR 4 , wherein: 
 M is a metal selected from the group consisting of: tungsten and molybdenum, 
 each of R 1 , R 2 , and R 3  are independently selected from the group consisting of: alkoxide, halide, oxide, nitride, and sulfide, and 
 R 4  is selected from the group consisting of: H, an aliphatic group having from 1 to 20 carbons, an aromatic group having from 1 to 20 carbons, and a heteroaryl group having from 1 to 20 carbons, wherein the heteroatom is selected from nitrogen, oxygen, boron, and sulfur. 
 
     
     
       2. The method of  claim 1 , wherein the mixture is substantially free of solvent. 
     
     
       3. The method of  claim 1 , wherein combining comprises combining the terminal alkyne as a solution having about 1 wt % or greater of the terminal alkyne. 
     
     
       4. The method of  claim 1 , wherein the terminal alkyne has the formula RC 2 H, wherein R is selected from the group consisting of: H, an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, an aromatic group having from 6 to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon atoms, and an alkynyl group having from 2 to 20 carbon atoms. 
     
     
       5. The method of  claim 4 , wherein R is substituted with a heteroatom selected from the group consisting of: halogen, oxygen, nitrogen, sulfur, silicon and combination(s) thereof. 
     
     
       6. The method of  claim 4 , wherein the terminal alkyne is selected from the group consisting of: phenylacetylene, 1-decyne, and combination(s) thereof. 
     
     
       7. The method of  claim 1 , wherein the alkylidyne catalyst compound is tris(t-butoxy)tungsten propylidyne. 
     
     
       8. The method of  claim 7 , wherein the alkylidyne catalyst compound is tris(t-butoxy)tungsten neopentylidyne. 
     
     
       9. The method of  claim 1 , wherein the reaction conditions comprise:
 a time of about 0.25 hours or greater; and 
 a temperature of about 25° C. or greater. 
 
     
     
       10. The method of  claim 1 , wherein a molar ratio of the terminal alkyne to the alkylidyne catalyst compound is about 100 or greater. 
     
     
       11. The method of  claim 10 , wherein the molar ratio is from about 250 to about 10,000. 
     
     
       12. The method of  claim 1 , further comprising:
 stirring the mixture; 
 quenching the mixture with a protic molecule; 
 flash evaporating excess monomer from the mixture by performing at least one of heating the mixture, applying a vacuum pressure, or combination(s) thereof; 
 optionally washing the mixture with a solvent; and 
 optionally collecting the ring polymer via filtration. 
 
     
     
       13. The method of  claim 1 , wherein a reaction yield of the ring polymer is about 20% or greater. 
     
     
       14. The method of  claim 1 , wherein a size of the ring polymer is from about 25 to about 75 mer units. 
     
     
       15. The method of  claim 1 , wherein the ring polymer has an Mw/Mn of about 1.5 to about 2. 
     
     
       16. A method of forming a ring polymer, comprising:
 forming a reaction mixture by:
 introducing an alkylidyne to a reaction vessel, wherein the alkylidyne has the formula (R 1 )(R 2 )(R 3 )MCR 4 , wherein: 
 M is a metal selected from the group consisting of: tungsten and molybdenum, 
 each of R 1 , R 2 , and R 3  is independently selected from the group consisting of: alkoxide, halide, oxide, nitride, and sulfide, and 
 R 4  is selected from the group consisting of: H, an aliphatic group having from 1 to 20 carbons, an aromatic group having from 1 to 20 carbons, and a heteroaryl group having from 1 to 20 carbons, wherein the heteroatom is selected from the group consisting of nitrogen, oxygen, boron, and sulfur; and 
 
 introducing a terminal alkyne to the reaction vessel; and 
 mixing the reaction mixture under reaction conditions to form the ring polymer. 
 
     
     
       17. The method of  claim 16 , wherein the terminal alkyne has the formula RC 2 H, wherein R is selected from the group consisting of: H, an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, an aromatic group having from 6 to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon atoms, and an alkynyl group having from 2 to 20 carbon atoms. 
     
     
       18. The method of  claim 17 , wherein the reaction conditions comprise:
 a time of about 8 hours or greater; and 
 a temperature of about 25° C. or greater. 
 
     
     
       19. A method of forming a ring polymer, comprising:
 forming a reaction mixture by:
 introducing an alkylidyne to a reaction vessel; and 
 introducing a terminal alkyne to the reaction vessel, wherein the terminal alkyne has the formula RC 2 H, wherein R is selected from the group consisting of: H, an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, an aromatic group having from 6 to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon atoms, and an alkynyl group having from 2 to 20 carbon atoms; and 
 
 mixing the reaction mixture under reaction conditions to form the ring polymer 
 wherein the alkylidyne has the formula (R 1 )(R 2 )(R 3 )MCR 4 , wherein:
 M is a metal selected from the group consisting of: tungsten and molybdenum, 
 each of R 1 , R 2 , and R 3  is independently selected from the group consisting of: alkoxide, halide, oxide, nitride, and sulfide, and 
 R 4  is selected from the group consisting of: H, an aliphatic group having from 1 to 20 carbons, an aromatic group having from 1 to 20 carbons, and a heteroaryl group having from 1 to 20 carbons, wherein the heteroatom is selected from the group consisting of nitrogen, oxygen, boron, and sulfur.